JP2019008001A - Photosensitive resin composition, photosensitive element, method for forming resist pattern and method for manufacturing printed wiring board - Google Patents

Abstract

To provide a photosensitive resin composition that has excellent adhesion and resolution, and sufficient photosensitivity, and can be used in an automatic cut laminator without trouble.SOLUTION: A photosensitive resin composition contains (A) a binder polymer having a styrene-derived structural unit, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a polyglycerol alkyl ester-type surfactant.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element, a resist pattern forming method, and a printed wiring board manufacturing method.

  Conventionally, in the field of manufacturing printed wiring boards, a photosensitive resin composition as a resist material used for etching treatment or plating treatment, and a photosensitive layer obtained using the photosensitive resin composition, a support, and a protective layer are included. Photosensitive elements are widely used.

  When manufacturing a wiring board using a photosensitive element, first, the photosensitive element is laminated on a substrate such as an insulating substrate covered with a copper foil while peeling the protective film, and a photosensitive resin composition is formed. Layers are stacked on the substrate. Next, after pattern exposure of the photosensitive layer through a mask film or the like, a resist pattern is formed by removing an unexposed portion of the photosensitive layer with a developer. Next, using this resist pattern as a mask, the substrate on which the resist pattern is formed is etched or plated to form a circuit pattern, and finally the cured portion (resist pattern) of the photosensitive layer is peeled off from the substrate.

  In such a method of manufacturing a wiring board, a laser direct drawing method in which actinic rays are directly irradiated in an image form using digital data without passing through a mask film has been put into practical use. As a light source used in the laser direct drawing method, a YAG laser, a semiconductor laser, or the like is used from the viewpoints of safety and handleability. Recently, a technique using a long-life, high-power gallium nitride blue laser as a light source has been proposed.

  Further, in recent years, a direct drawing method called a DLP (Digital Light Processing) exposure method capable of forming a finer pattern (fine pattern) than the conventional one has been introduced with higher definition and higher density of a wiring board. In general, in the DLP exposure method, active light having a wavelength of 390 nm to 430 nm using a blue-violet semiconductor laser as a light source is used. In addition, an exposure method using a polygon multi-beam having a wavelength of 355 nm using a YAG laser as a light source, which can deal with a small variety of products in general-purpose printed wiring boards, is also used.

  The resist material used in the direct drawing exposure method requires a low exposure amount and alkali resistance at a low degree of cure from the viewpoint of throughput per unit time (throughput). In many cases (see, for example, Patent Documents 1 to 3).

Japanese Patent No. 3406526 International Publication No. 2015/098870 International Publication No. 2017/043544

  However, if a compound having a rigid skeleton is added to improve adhesion and resolution, when a plurality of photosensitive elements are laminated on a substrate with an auto-cut laminator, there is a problem that lamination cannot be performed in the middle. I understood. Specifically, problems such as wrinkling of the photosensitive element and the inability to extend the photosensitive element occur.

  The present invention has been made in view of the above problems, a photosensitive resin composition having excellent adhesion and resolution, sufficient photosensitivity, and usable with no problem with an auto-cut laminator, and It is an object of the present invention to provide a photosensitive element, a resist pattern forming method, and a printed wiring board manufacturing method.

  In order to solve the above problems, the present inventors have intensively studied. As a result, a binder polymer having a structural unit derived from styrene, a photopolymerizable compound, a photopolymerization initiator, and a polyglycerin alkyl ester type surfactant. In combination with the above, it has been found that a resist pattern excellent in resolution and adhesion can be formed with excellent sensitivity, and a photosensitive resin composition that can be used without any problem with an auto-cut laminator can be obtained. It came to be completed.

  The present invention includes (A) a binder polymer having a structural unit derived from styrene, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a polyglycerol alkyl ester type surfactant. , A photosensitive resin composition is provided.

  According to the said photosensitive resin composition, the resist pattern which is excellent in resolution and adhesiveness can be formed with the outstanding sensitivity. The said photosensitive resin composition can be used without a problem with an auto cut laminator.

［式（Ｉ）中、Ｒ^１及びＲ^２はそれぞれ独立に、水素原子又はメチル基を示す。ＸＯ及びＹＯはそれぞれ独立に、エチレンオキシ基又はプロピレンオキシ基を示す。（ＸＯ）ｒ_１、（ＸＯ）ｒ_２、（ＹＯ）ｓ_１、及び（ＹＯ）ｓ_２はそれぞれ（ポリ）エチレンオキシ基又は（ポリ）プロピレンオキシ基を示す。ｒ_１、ｒ_２、ｓ_１及びｓ_２はそれぞれ独立に、０〜４０を示す。ｒ_１、ｒ_２、ｓ_１及びｓ_２は構造単位の構造単位数を示す。従って単一の分子においては整数値を示し、複数種の分子の集合体としては平均値である有理数を示す。以下、構造単位の構造単位数については同様である。］ In the photosensitive resin composition of the present invention, the photopolymerizable compound (B) is represented by the following general formula (I) from the viewpoint of further improving sensitivity and resolution and adhesion of the resist pattern to be formed. It is preferable that the compound is included.

[In Formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an ethyleneoxy group or a propyleneoxy group. _(XO) r _1, showing the _{(XO) r 2, (YO} ) s 1, and (YO) _{s 2,} respectively (poly) ethyleneoxy group or a (poly) propyleneoxy group. _{r 1,} r 2, _{s 1} and _{s 2} each independently represent 0-40. r ₁ , r ₂ , s ₁ and s ₂ represent the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the same applies to the number of structural units. ]

  The present invention also provides a photosensitive element comprising a support and a photosensitive layer formed from the photosensitive resin composition provided on the support. By using such a photosensitive element, in particular, a resist pattern excellent in resolution and adhesion can be efficiently formed with excellent sensitivity.

  The present invention also includes a photosensitive layer forming step of forming a photosensitive layer on a substrate using the photosensitive resin composition or the photosensitive element, and irradiating at least a part of the photosensitive layer with actinic rays. There is provided a resist pattern forming method comprising: an exposure step of curing the region; and a developing step of removing an unexposed portion other than the region of the photosensitive layer from the substrate. According to the above method for producing a substrate with a resist pattern, a resist pattern having excellent resolution and adhesion can be efficiently formed with excellent sensitivity.

  The present invention also provides a method for producing a printed wiring board, including a step of etching or plating a substrate on which a resist pattern is formed by the method for producing a substrate with a resist pattern. According to this manufacturing method, a printed wiring board having high-density wiring such as a high-density package substrate can be efficiently manufactured with excellent accuracy and high productivity.

  According to the present invention, a resist pattern that is excellent in resolution and adhesion can be formed with excellent sensitivity, a photosensitive resin composition that can be used without problems in an auto-cut laminator, and a photosensitive element using the same, A method for manufacturing a substrate with a resist pattern and a method for manufacturing a printed wiring board can be provided.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In this specification, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or methacrylate, and (meth) acryloyloxy group means acryloyloxy group. Or means a methacryloyloxy group. (Poly) ethyleneoxy group means at least one ethyleneoxy group or polyethyleneoxy group in which two or more ethylene groups are linked by an ether bond. (Poly) propyleneoxy group means at least one propyleneoxy group or a polypropyleneoxy group in which two or more propylene groups are linked by an ether bond. Furthermore, “EO-modified” means a compound having a (poly) ethyleneoxy group, and “PO-modified” means a compound having a (poly) propyleneoxy group. “PO-modified” means a compound having both a (poly) ethyleneoxy group and a (poly) propyleneoxy group.

  In addition, in this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included. In the present specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.

  Further, in the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means.

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment includes (A) a binder polymer having a structural unit derived from styrene, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a polyglycerin alkyl. And an ester type surfactant. The photosensitive resin composition may further contain other components as necessary.

(A) component: binder polymer (A) As a binder polymer, for example, acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, epoxy resin and (meta ) Epoxy acrylate resin obtained by reaction of acrylic acid, acid-modified epoxy acrylate resin obtained by reaction of epoxy acrylate resin and acid anhydride, and the like. These resins can be used singly or in combination of two or more. From the viewpoint of excellent alkali developability and film formability, it is preferable to use an acrylic resin, and the acrylic resin is a structural unit derived from (a1) (meth) acrylic acid and (a2) (meth) acrylic acid alkyl ester. It is more preferable to contain the derived structural unit. Here, “acrylic resin” means a polymer mainly having monomer units derived from a polymerizable monomer having a (meth) acrylic group.

  The binder polymer, for example, as a polymerizable monomer (monomer), (meth) acrylic acid, (meth) acrylic acid alkyl ester and other polymerizable monomers used as necessary, by a conventional method, It can be obtained by radical polymerization.

  The content of the structural unit derived from (a1) (meth) acrylic acid in the binder polymer is derived from the polymerizable monomer constituting the binder polymer from the viewpoint of effectively exhibiting developability and peeling properties. 1 mass% to 99 mass% is preferable, more preferably 5 mass% to 80 mass% is more preferable, and 10 mass% to 60 mass% based on the total mass of the structural units to be performed (100 mass%, the same applies hereinafter). It is more preferable that it is mass%, and it is especially preferable that it is 15 mass%-50 mass%.

  (A2) As the (meth) acrylic acid alkyl ester, a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms is preferable, and an (meth) acrylic acid alkyl having an alkyl group having 1 to 8 carbon atoms Esters are more preferred. Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic. Hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, (meth) An example is dodecyl acrylate. These can be used individually by 1 type or in combination of 2 or more types.

  (A2) The content of structural units derived from (meth) acrylic acid alkyl esters is such that all of the structural units derived from the polymerizable monomers constituting the binder polymer are excellent in peelability, resolution and adhesion. It is preferably 1% by mass to 50% by mass based on mass (100% by mass), more preferably 1% by mass to 30% by mass, still more preferably 1% by mass to 20% by mass, It is especially preferable that it is 2 mass%-10 mass%. In terms of excellent peelability, the content is preferably 1% by mass or more, and more preferably 2% by mass or more. Further, in terms of excellent resolution and adhesion, the content is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less. It is particularly preferable that the content is not more than mass%.

  The copolymer may further contain other monomer that can be copolymerized with the component (a1) and / or the component (a2) in the structural unit.

  Other monomers that can be copolymerized with the component (a1) and / or the component (a2) are not particularly limited. For example, benzyl (meth) acrylate, cycloalkyl ester (meth) acrylate, benzyl derivative (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, ( Adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( (Meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobol (meth) acrylate Nyloxyethyl, (meth) acryl Cyclohexyloxyethyl acid, adamantyloxyethyl (meth) acrylate, dicyclopentenyloxypropyloxyethyl (meth) acrylate, dicyclopentanyloxypropyloxyethyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate (Meth) acrylic acid esters such as propyloxyethyl, adamantyloxypropyloxyethyl (meth) acrylate; α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) (Meth) acrylic acid derivatives such as acrylic acid; polymerizable styrene derivatives substituted at the α-position or aromatic ring such as vinyl toluene and α-methylstyrene; acrylamides such as diacetone acrylamide; acrylonitrile; vinyl-n -Bu Ether compounds of vinyl alcohol such as ether; maleic acid; maleic anhydride; maleic monoesters such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itacone And unsaturated carboxylic acid derivatives such as acid, crotonic acid, and propiolic acid. These can be used individually by 1 type or in combination of 2 or more types.

  The binder polymer of the present invention further has a structural unit derived from styrene from the viewpoint of improving resolution.

  The content of the structural unit derived from styrene in the binder polymer is based on the total mass of the structural unit derived from the polymerizable monomer constituting the binder polymer from the viewpoint of excellent resolution and peelability (100 % By mass, the same applies hereinafter), preferably 3% by mass to 85% by mass, more preferably 5% by mass to 75% by mass, still more preferably 10% by mass to 70% by mass. It is especially preferable that it is 50 mass%-50 mass%. From the viewpoint of excellent resolution, the content is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. Moreover, from the point which is excellent in peelability and adhesiveness, it is preferable that this content rate is 85 mass% or less, It is more preferable that it is 75 mass% or less, It is further more preferable that it is 70 mass% or less, 50 It is particularly preferable that the content is not more than mass%.

  The acid value of the binder polymer is preferably 90 mgKOH / g to 250 mgKOH / g, more preferably 100 mgKOH / g to 240 mgKOH / g, and more preferably 120 mgKOH / g to 235 mgKOH / g in terms of excellent developability and adhesion. g is more preferable, and 130 mgKOH / g to 230 mgKOH / g is particularly preferable. From the viewpoint of shortening the development time, the acid value is preferably 90 mgKOH / g or more, more preferably 100 mgKOH / g or more, further preferably 120 mgKOH / g or more, and 130 mgKOH / g or more. It is particularly preferred. From the viewpoint of sufficiently achieving the adhesion of the cured product of the photosensitive resin composition, the acid value is preferably 250 mgKOH / g or less, more preferably 240 mgKOH / g or less, and 235 mgKOH / g or less. It is more preferable that it is 230 mgKOH / g or less.

The acid value of the binder polymer as the component (A) can be measured as follows. That is, first, 1 g of the binder polymer that is the object of acid value measurement is precisely weighed. 30 g of acetone is added to the precisely weighed binder polymer and dissolved uniformly. Next, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1N potassium hydroxide (KOH) aqueous solution. The acid value is determined by calculating the number of mg of KOH required to neutralize the acetone solution of the binder polymer to be measured. When a solution obtained by mixing a binder polymer with a synthetic solvent, a diluting solvent, or the like is an object to be measured, the acid value is calculated by the following formula.
Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100)
In the formula, Vf represents the titration amount (mL) of the aqueous KOH solution, Wp represents the mass (g) of the solution containing the measured binder polymer, and I represents the ratio of the nonvolatile content in the solution containing the measured binder polymer. (Mass%) is shown.
In addition, when blending the binder polymer in a state mixed with volatile components such as a synthetic solvent and a diluting solvent, the mixture is preliminarily heated for 1 to 4 hours at a temperature higher than the boiling point of the volatile components by 1 to 4 hours before being volatile. The acid value can also be measured after removing the component.

  The weight average molecular weight (Mw) of the binder polymer is 10,000 to 200,000 in terms of excellent developability and adhesion when measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene). It is preferably 15000 to 100,000, more preferably 20000 to 80000, and particularly preferably 23,000 to 60000. In terms of excellent developability, it is preferably 200000 or less, more preferably 100000 or less, still more preferably 80000 or less, and particularly preferably 60000 or less. In terms of excellent adhesion, it is preferably 10,000 or more, more preferably 15,000 or more, further preferably 20,000 or more, and particularly preferably 23,000 or more.

The GPC calibration curve is approximated by a cubic equation using a standard polystyrene 5 sample set (PStQuick MP-H, PStQuick B [trade name, manufactured by Tosoh Corp.]). The GPC conditions are shown below.
Apparatus: (Pump: L-2130 type [manufactured by Hitachi High-Technologies Corporation]), (Detector: L-2490 type RI [manufactured by Hitachi High-Technologies Corporation]), (Column oven: L-2350 [( Made by Hitachi High-Technologies Corporation]])
Column: Gelpack GL-R440 + Gelpack GL-R450 + Gelpack GL-R400M (three in total) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
Column size: 10.7 mmI. D. × 300mm
・ Eluent: Tetrahydrofuran ・ Sample concentration: 10 mg / 2 mL
・ Injection volume: 200 μL
・ Flow rate: 2.05 mL / min ・ Measurement temperature: 25 ° C.

  The degree of dispersion (weight average molecular weight / number average molecular weight) of the binder polymer is preferably 3.0 or less, more preferably 2.8 or less, in view of excellent resolution and adhesion. More preferably, it is 5 or less.

  The binder polymer may have a characteristic group in its molecule that has photosensitivity to light having a wavelength in the range of 340 nm to 430 nm, if necessary. Examples of the characteristic group include a group constituted by removing at least one hydrogen atom from a sensitizer described later.

  The content of the component (A) in the photosensitive resin composition is 30 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B) in terms of excellent film formability, sensitivity, and resolution. It is preferably ˜70 parts by mass, more preferably 35 parts by mass to 65 parts by mass, and particularly preferably 40 parts by mass to 60 parts by mass. From the viewpoint of formability of the film (photosensitive layer), the content is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, and further preferably 40 parts by mass or more. Further, from the viewpoint of sufficiently obtaining sensitivity and resolution, the content is preferably 70 parts by mass or less, more preferably 65 parts by mass or less, and further preferably 60 parts by mass or less. preferable.

  As the photopolymerizable compound as component (B), a photopolymerizable compound having an ethylenically unsaturated group can be used.

  The said photosensitive resin composition contains the compound which has an ethylenically unsaturated bond group as (B) component. The compound having an ethylenically unsaturated bond group includes a compound having one ethylenically unsaturated bond group in the molecule, a compound having two ethylenically unsaturated bond groups in the molecule, and an ethylenically unsaturated bond in the molecule. Examples thereof include compounds having 3 or more groups.

  It is preferable that the said (B) component contains at least 1 sort (s) of the compound which has two ethylenically unsaturated bond groups in a molecule | numerator as a photopolymerizable compound. When the component (B) contains a compound having two ethylenically unsaturated bond groups in the molecule as the photopolymerizable compound, the content thereof is in 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably 5 parts by mass to 70 parts by mass, more preferably 5 parts by mass to 65 parts by mass, and still more preferably 10 parts by mass to 60 parts by mass.

  Examples of the compound having two ethylenically unsaturated bond groups in the molecule include a bisphenol type di (meth) acrylate compound, a hydrogenated bisphenol A di (meth) acrylate compound, and a di (meta) having a urethane bond in the molecule. ) Acrylate compound, polyalkylene glycol di (meth) acrylate having both (poly) ethyleneoxy group and (poly) propyleneoxy group in the molecule, and trimethylolpropane di (meth) acrylate.

  The above component (B) is a photopolymerizable compound, and from the viewpoint of improving resolution and peeling properties, a bisphenol-type di (meth) acrylate compound, a hydrogenated bisphenol A-based di (meth) acrylate compound, and (poly ) Containing at least one compound having two ethylenically unsaturated bond groups in the molecule selected from the group consisting of polyalkylene glycol di (meth) acrylates having an ethyleneoxy group and a (poly) propyleneoxy group. Preferably, the bisphenol-type di (meth) acrylate compound contains at least one bisphenol-type di (meth) acrylate compound, has an ethyleneoxy group, and the number of structural units of the ethyleneoxy group is 8 or less. More preferably, at least one kind is included.

［上記一般式（Ｉ）中、Ｒ^１及びＲ^２はそれぞれ独立に、水素原子又はメチル基を示す。ＸＯ及びＹＯはそれぞれ独立に、エチレンオキシ基又はプロピレンオキシ基を示す。（ＸＯ）ｒ_１、（ＸＯ）ｒ_２、（ＹＯ）ｓ_１、及び（ＹＯ）ｓ_２はそれぞれ（ポリ）エチレンオキシ基又は（ポリ）プロピレンオキシ基を示す。ｒ_１、ｒ_２、ｓ_１及びｓ_２はそれぞれ独立に、０〜４０を示す。ｒ_１、ｒ_２、ｓ_１及びｓ_２は構造単位の構造単位数を示す。従って単一の分子においては整数値を示し、複数種の分子の集合体としては平均値である有理数を示す。以下、構造単位の構造単位数については同様である。］ Examples of the bisphenol-type di (meth) acrylate compound include compounds represented by the following general formula (I).

[In the general formula (I), R ¹ and R ² each independently represents a hydrogen atom or a methyl group. XO and YO each independently represent an ethyleneoxy group or a propyleneoxy group. _(XO) r _1, shows a _{(XO) r 2, (YO} ) s 1, and (YO) _{s 2,} respectively (poly) ethyleneoxy group or a (poly) propyleneoxy group. _{r 1,} r 2, _{s 1} and _{s 2} each independently represent 0-40. r ₁ , r ₂ , s ₁ and s ₂ represent the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the same applies to the number of structural units. ]

  When the compound has a propyleneoxy group, the total number of structural units of the propyleneoxy group in the compound is preferably 2 or more, more preferably 3 or more from the viewpoint of excellent resist resolution. . Moreover, it is preferable that it is 5 or less from a developable viewpoint.

  When the compound has an ethyleneoxy group, the total number of structural units of the ethyleneoxy group in the compound is preferably 4 or more, more preferably 6 or more, from the viewpoint of excellent developability. More preferably, it is 8 or more. Moreover, it is preferable that it is 16 or less from a viewpoint of resolution, and it is more preferable that it is 14 or less.

  Among the compounds represented by the above general formula (I), 2,2-bis (4- (methacryloxide decaethoxytetrapropoxy) phenyl) propane is FA-3200MY (manufactured by Hitachi Chemical Co., Ltd., product name), 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane is commercially available as FA-324M (manufactured by Hitachi Chemical Co., Ltd., product name), and 2,2-bis (4- (Methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) or FA-321M (manufactured by Hitachi Chemical Co., Ltd., product name). 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name).These may be used alone or in any combination of two or more.

  When the photosensitive resin composition contains a bisphenol type di (meth) acrylate compound as the component (B), the content thereof is 1 part by mass in 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably ~ 65 parts by mass, more preferably 5 parts by mass to 60 parts by mass, and still more preferably 10 parts by mass to 55 parts by mass.

  Examples of the hydrogenated bisphenol A di (meth) acrylate compound include 2,2-bis (4- (methacryloxypentaethoxy) cyclohexyl) propane. When the said photosensitive resin composition contains hydrogenated bisphenol A type | system | group di (meth) acrylate compound, as the content, 1 mass part-50 in 100 mass parts of total amounts of (A) component and (B) component. It is preferable that it is a mass part, and it is more preferable that it is 5 mass parts-40 mass parts.

  The component (B) may contain at least one photopolymerizable compound having three or more ethylenically unsaturated bond groups in the molecule as the photopolymerizable compound.

  Examples of the compound having three or more ethylenically unsaturated bond groups include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate (one having 1 to 5 structural units of ethyleneoxy group) ), PO-modified trimethylolpropane tri (meth) acrylate, EO and PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate and tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) Examples include acrylate, ethoxylated pentaerythritol tetraacrylate, or dipentaerythritol hexa (meth) acrylate. These can be used alone or in combination of two or more.

  Tetramethylol methane triacrylate is A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name), and EO-modified trimethylol propane trimethacrylate is TMPT21E and TMPT30E (manufactured by Hitachi Chemical Co., Ltd., sample name). Pentaerythritol triacrylate is SR444 (product name, manufactured by Sartomer Co., Ltd.), and dipentaerythritol hexaacrylate is A-DPH (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethoxylated pentaerythritol. Tetraacrylate is commercially available as ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)).

  When the component (B) includes a photopolymerizable compound having three or more ethylenically unsaturated bond groups in the molecule as the photopolymerizable compound, the content thereof is resolution, adhesion, resist shape, and From the viewpoint of improving the peeling characteristics after curing in a well-balanced manner, the total amount of the component (A) and the component (B) is preferably 3 parts by mass to 30 parts by mass, and preferably 5 parts by mass to 25 parts by mass. It is more preferable that it is 5 mass parts-20 mass parts.

  The above component (B) is ethylenically in the molecule as another photopolymerizable compound from the viewpoint of improving the resolution, adhesion, resist shape and release properties after curing in a well-balanced manner or suppressing the occurrence of scum. You may include the photopolymerizable compound which has one unsaturated bond group.

  Examples of the photopolymerizable compound having one ethylenically unsaturated bond group in the molecule include nonylphenoxypolyethyleneoxyacrylate, phthalic acid compound, and (meth) acrylic acid alkyl ester. Among the above, it is preferable that nonylphenoxypolyethyleneoxyacrylate or a phthalic acid compound is included from the viewpoint of improving the resolution, adhesion, resist shape, and peeling property after curing in a well-balanced manner.

  When the component (B) includes a photopolymerizable compound having one ethylenically unsaturated bond group in the molecule as the photopolymerizable compound, the content thereof is a total of 100 components (A) and (B). The mass part is preferably 1 part by mass to 20 parts by mass, more preferably 3 parts by mass to 15 parts by mass, and still more preferably 5 parts by mass to 12 parts by mass.

  The total content of the component (B) in the photosensitive resin composition is preferably 30 parts by mass to 70 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B), and 35 parts by mass. It is more preferable to set it as -65 mass parts, and it is especially preferable to set it as 35 mass parts-60 mass parts. When the content is 30 parts by mass or more, sufficient sensitivity and resolution tend to be easily obtained. When the content is 70 parts by mass or less, a film (photosensitive layer) tends to be easily formed, and a good resist shape tends to be easily obtained.

Component (C): Photopolymerization initiator The photosensitive resin composition contains at least one photopolymerization initiator as the component (C). There is no restriction | limiting in particular as a photoinitiator, It can select from the photoinitiator used normally, and can use it suitably. Among these, the component (C) preferably contains an acridine compound having one or two acridinyl groups in one molecule. That is, the component (C) is composed of an acridine compound having two acridinyl groups (hereinafter also referred to as “(C1) compound”) and an acridine compound having one acridinyl group (hereinafter also referred to as “(C2) compound”). It is preferable that at least one compound selected from the group consisting of:

Examples of the compound (C1) include acridine compounds represented by the following general formula (II).

In the formula (II), R ³ represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms. R ³ is preferably an alkylene group having 2 to 20 carbon atoms, and more preferably an alkylene group having 4 to 14 carbon atoms, from the viewpoint of more reliably obtaining the effect exhibited by the photosensitive resin composition.

  Examples of the compound represented by the general formula (II) include 1,2-di (9-acridinyl) ethane, 1,3-di (9-acridinyl) propane, 1,4-di (9-acridinyl). Butane, 1,5-di (9-acridinyl) pentane, 1,6-di (9-acridinyl) hexane, 1,7-di (9-acridinyl) heptane, 1,8-di (9-acridinyl) octane, 1,9-di (9-acridinyl) nonane, 1,10-di (9-acridinyl) decane, 1,11-di (9-acridinyl) undecane, 1,12-di (9-acridinyl) dodecane, 1, 14-di (9-acridinyl) tetradecane, 1,16-di (9-acridinyl) hexadecane, 1,18-di (9-acridinyl) octadecane, 1,20-di (9-acridinyl) Ai Di (9-acridinyl) alkanes such as Sun; di (9-acridinyl) such as 1,3-di (9-acridinyl) -2-oxapropane, 1,5-di (9-acridinyl) -3-oxapentane Oxalkane; Di (9-acridinyl) thioalkane such as 1,3-di (9-acridinyl) -2-thiapropane and 1,5-di (9-acridinyl) -3-thiapentane. These are used individually by 1 type or in combination of 2 or more types.

From the standpoint of improving photosensitivity and resolution, as the (C1) compound, an acridine compound in which R ³ in the formula (II) is a heptylene group (for example, product name “N-1717” manufactured by ADEKA Corporation) ) Is preferably included.

  When the photosensitive resin composition contains the (C1) compound as a photopolymerization initiator, the content of the (C1) compound is (A) and (B) from the viewpoints of sensitivity, resolution, and adhesion. For example, it may be 0.1 to 10 parts by mass or 0.5 to 5 parts by mass, and preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the total amount of components. 0.25 parts by mass to 1.5 parts by mass, more preferably 0.35 parts by mass to 1.2 parts by mass, and 0.45 parts by mass to 1 part by mass. Particularly preferred. When the content of the (C1) compound is 0.1 parts by mass or more, better sensitivity, resolution, or adhesion tends to be obtained. When the amount is 10 parts by mass or less, a better resist shape tends to be obtained, and when the amount is 2 parts by mass or less, a tendency to obtain a better resist shape is remarkable.

  Examples of the compound (C2) include acridine compounds represented by the following general formula (III).

In formula (III), R ⁴ represents a halogen atom, an amino group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkylamino group having 1 to 6 carbon atoms. m shows the integer of 0-5. When m is 2 or more, the plurality of R ⁴ may be the same or different.

  Examples of the acridine compound represented by the general formula (III) include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine, 9- (p-chlorophenyl) acridine. , 9- (m-chlorophenyl) acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine and 9-pentylaminoacridine. These are used individually by 1 type or in combination of 2 or more types.

  When the photosensitive resin composition contains the compound (C2) as a photopolymerization initiator, the content of the compound (C2) is from the viewpoint of sensitivity, resolution, and adhesion, and the components (A) and (B) For example, it may be 0.1 to 10 parts by mass or 0.5 to 5 parts by mass, and preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the total amount of components. 0.3 parts by mass to 1.5 parts by mass, more preferably 0.4 parts by mass to 1.2 parts by mass, and further preferably 0.5 parts by mass to 0.8 parts by mass. It is particularly preferred. When the content of the (C2) compound is 0.1 parts by mass or more, better sensitivity, resolution, or adhesion tends to be obtained. When the amount is 10 parts by mass or less, a better resist shape tends to be obtained, and when the amount is 2 parts by mass or less, a tendency to obtain a better resist shape is remarkable.

  From the viewpoint of improving sensitivity, the photosensitive resin composition preferably also contains a (C3) compound represented by the following general formula (IV) as the component (C). The (C3) compound represented by the general formula (IV) can be said to be N-phenylglycine.

  When the photosensitive resin composition contains the (C3) compound as a photopolymerization initiator, the upper limit of the content of the (C3) compound is from the viewpoint of improving the resolution (A) component and (B) The total amount of components is preferably 0.1 parts by mass or less, more preferably 0.07 parts by mass or less, and still more preferably 0.06 parts by mass or less. (C3) 0.01 mass part or more, 0.02 mass part or more, and 0.04 mass part or more may be sufficient from the viewpoint of improving a sensitivity and adhesiveness. There exists a tendency for better resolution to be acquired as it is 0.1 mass part or less. Moreover, a sensitivity, resolution, and adhesiveness can be improved with sufficient balance by being 0.01-0.1 mass part.

  The said photosensitive resin composition may contain photoinitiators other than the said (C1), (C2) compound, and (C3) compound as (C) component.

  As photopolymerization initiators other than the (C1) compound, the (C2) compound and the (C3) compound, benzophenone, N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N , N, N ′, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- Aromatic ketone compounds such as 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthra Non, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, etc. Quinone compounds; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenyl 2,4,5-triarylimidazole dimer such as dazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; benzyl derivative such as benzyldimethyl ketal; 9,10- Substituted anthracene compounds such as dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentoxyanthracene; coumarin compounds; oxazole compounds; pyrazoline compounds; Triarylamine compounds; and the like. These photoinitiators can be used individually by 1 type or in combination of 2 or more types. Moreover, it is good also as a photoinitiator combining a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and a dimethylamino benzoic acid.

  The 2,4,5-triarylimidazole dimer is a symmetric compound in which the aryl group substituents of the two 2,4,5-triarylimidazoles constituting the dimer are the same. They may be different or asymmetrical compounds.

  When the photosensitive resin composition contains a photopolymerization initiator other than the (C1) compound, the (C2) compound and the (C3) compound as the component (C), the content thereof is a viewpoint of sensitivity and internal photocurability. From 0.01 part by weight to 10 parts by weight, more preferably from 0.1 part by weight to 7 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). More preferably, it is 0.2-5 mass parts.

  (C) Content of a component is 0.01 mass part-20 mass parts with respect to a total amount of 100 mass parts of (A) component and (B) component from a viewpoint of a sensitivity, adhesiveness, and internal photocurability. It is preferable that it is 0.05 mass part-10 mass parts, and it is still more preferable that it is 0.1 mass part-5 mass parts.

  The photosensitive resin composition is at least one selected from the group consisting of a compound (C1) and a compound (C2) as the component (C), preferably (C1), from the viewpoints of sensitivity, adhesion, and internal photocurability. ) Compound, and the content thereof is preferably 0.1 parts by mass to 10 parts by mass, and 0.2 parts by mass to 5 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It is more preferable that

(D) Component: Polyglycerin alkyl ester type surfactant A known polyglycerin alkyl ester type surfactant can be used. These may be used alone or in combination of two or more.

  The content of the component (D) is preferably 5 parts by mass or less with respect to 100 parts by mass of the total amount of the component (A) and the component (B) from the viewpoints of sensitivity, adhesion, and internal photocurability. 0.001 to 3 parts by mass is more preferable, and 0.01 to 1 part by mass is particularly preferable. In terms of laminating properties, it is preferably 0.01 parts by mass or more, and in terms of excellent resolution and adhesion, it is preferably 1 part by mass or less.

[Other ingredients]
The above-mentioned photosensitive resin composition may be a dye such as malachite green, Victoria pure blue, brilliant green, or methyl violet, if necessary; leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, o-chloroaniline, etc. Photo-coloring agent; thermal coloring inhibitor; plasticizer such as p-toluenesulfonamide; pigment; filler; antifoaming agent; flame retardant; adhesion-imparting agent; leveling agent; Other additives such as an agent, a fragrance, an imaging agent, and a thermal crosslinking agent may be further included.

  When the said photosensitive resin composition contains another additive, the content can be suitably selected according to the objective etc. For example, it can be contained in an amount of about 0.01 to 20 parts by mass per 100 parts by mass of the total amount of component (A) and component (B). These additives can be used alone or in combination of two or more.

[Solution of photosensitive resin composition]
The photosensitive resin composition of this embodiment may further contain at least one organic solvent in order to adjust the viscosity as necessary. Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; N, N- And aprotic polar solvents such as dimethylformamide. These may be used alone or in combination of two or more. The content of the organic solvent contained in the photosensitive resin composition can be appropriately selected depending on the purpose and the like. For example, the photosensitive resin composition can be used as a solution having a solid content of about 30% by mass to 60% by mass. Hereinafter, the photosensitive resin composition containing the organic solvent is also referred to as “coating liquid”.

  A photosensitive layer can be formed using the photosensitive resin composition by applying (for example, applying) the coating liquid onto the surface of a support, a metal plate, or the like described later and drying the coating liquid. It does not restrict | limit especially as a metal plate, According to the objective etc., it can select suitably. Examples of the metal plate include metal plates such as copper, copper-containing alloys, iron-containing alloys such as nickel, chromium, iron, and stainless steel. As a metal plate, Preferably, metal plates, such as copper, a copper containing alloy, and an iron containing alloy, are mentioned.

  The thickness of the photosensitive layer to be formed is not particularly limited and can be appropriately selected depending on the application. For example, the thickness after drying is preferably 1 μm to 100 μm. When the photosensitive layer is formed on the metal plate, the surface of the photosensitive layer opposite to the metal plate may be covered with a protective layer. Examples of the protective layer include polymer films such as polyethylene and polypropylene.

  The photosensitive resin composition can be applied to the formation of a photosensitive layer of a photosensitive element described later. That is, another embodiment of the present invention includes (A) a binder polymer having a structural unit derived from styrene, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a polyglycerin alkyl ester. Application of a photosensitive resin composition containing a type surfactant to a photosensitive element.

  Moreover, the photosensitive resin composition of this embodiment can be used for the formation method of the resist pattern mentioned later. That is, another embodiment of the present invention includes (A) a binder polymer having a structural unit derived from styrene, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a polyglycerin alkyl ester. It is application to the formation method of the resist pattern of the photosensitive resin composition containing type | mold surfactant.

[Photosensitive element]
The photosensitive element of this invention is equipped with a support body and the photosensitive layer formed from the said photosensitive resin composition provided on this support body. The photosensitive layer may be a coating film. The coating film as used in the present specification is that in which the photosensitive resin composition is in an uncured state. The photosensitive element may have other layers, such as a protective layer, as needed.

  As the support, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polyolefin such as polypropylene and polyethylene can be used.

  The thickness of the support (polymer film) is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, and still more preferably 5 μm to 30 μm. It can suppress that a support body is torn when peeling a support body because the thickness of a support body is 1 micrometer or more. Moreover, the fall of resolution is suppressed by being 100 micrometers or less.

  The protective layer preferably has a smaller adhesive force to the photosensitive layer than the adhesive force of the support to the photosensitive layer. A low fisheye film is preferred. Here, “fish eye” means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, the “low fish eye” means that there are few foreign matters in the film.

  Specifically, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polyolefin such as polypropylene and polyethylene can be used as the protective layer. Commercially available products include polypropylene films such as Oji Paper's Alphan MA-410 and E-200, Shin-Etsu Film Co., Ltd., and PS series polyethylene terephthalate films such as Teijin's PS-25. It is done. The protective layer 4 may be the same as the support 2.

  The thickness of the protective layer is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, still more preferably 5 μm to 30 μm, and particularly preferably 15 μm to 30 μm. When the thickness of the protective layer is 1 μm or more, the protective layer can be prevented from being broken when the photosensitive layer and the support are laminated on the substrate while peeling off the protective layer. When it is 100 μm or less, it is excellent in handleability and inexpensiveness.

  Specifically, the photosensitive element of this embodiment can be manufactured as follows, for example. (A) a binder polymer having a structural unit derived from styrene, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a polyglycerol alkyl ester type surfactant, an organic solvent A step of preparing a coating solution dissolved in a solution, a step of applying (e.g., coating) the coating solution on a support to form a coating layer, a step of drying the coating layer to form a photosensitive layer, It can manufacture with the manufacturing method containing.

Application of the solution of the photosensitive resin composition onto the support can be performed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.

  The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it is preferably dried at 70 ° C. to 150 ° C. for 5 minutes to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive layer is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step.

  The thickness of the photosensitive layer in the photosensitive element can be appropriately selected depending on the application. The thickness after drying is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and still more preferably 5 μm to 40 μm. Industrial coating becomes easy because the thickness of a photosensitive layer is 1 micrometer or more. When the thickness is 100 μm or less, adhesion and resolution tend to be sufficiently obtained.

  The transmittance of the photosensitive layer with respect to ultraviolet rays is preferably 5% to 75%, more preferably 10% to 65%, and more preferably 15% to 55% with respect to ultraviolet rays in the wavelength range of 350 nm to 420 nm. More preferably. When the transmittance is 5% or more, sufficient adhesion tends to be obtained. When it is 75% or less, sufficient resolution tends to be easily obtained. The transmittance can be measured with a UV spectrometer. An example of the UV spectrometer is a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

  The photosensitive element may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. As these intermediate layers, for example, the intermediate layers described in JP-A-2006-098982 can also be applied in the present invention.

  The form of the obtained photosensitive element is not particularly limited. For example, it may be in the form of a sheet, or may be in the form of a roll wound around a core. When it winds up in roll shape, it is preferable to wind up so that a support body may become an outer side. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). From the viewpoint of end face protection, it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained, and it is preferable to install a moisture-proof end face separator from the standpoint of edge fusion resistance. As a packaging method, it is preferable to wrap and package in a black sheet with low moisture permeability.

  The photosensitive element of this embodiment can be used suitably for the formation method of the resist pattern mentioned later, for example.

[Method of forming resist pattern]
A resist pattern can be formed using the photosensitive resin composition. The resist pattern forming method of this embodiment includes (i) a photosensitive layer forming step of forming a photosensitive layer on the substrate using the photosensitive resin composition, and (ii) at least a partial region of the photosensitive layer. An exposure step of irradiating actinic light to form a cured product region by photocuring the region; and (iii) removing the region other than the cured product region of the photosensitive layer from the substrate, And a developing step for forming a resist pattern which is the cured product region. The method for forming a resist pattern may further include other steps as necessary, and the photosensitive layer in the photosensitive layer forming step may be a coating film.

(I) Photosensitive layer forming step First, a photosensitive layer is formed on a substrate using the photosensitive resin composition. As the substrate, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used.

  For example, when the photosensitive element has a protective layer, the photosensitive layer is formed by pressing the photosensitive layer of the photosensitive element while heating the photosensitive layer after the protective layer is removed. Is done. Thereby, a laminate in which the substrate, the photosensitive layer, and the support are laminated in this order is obtained.

This photosensitive layer forming step is preferably performed under reduced pressure from the viewpoint of adhesion and followability. Photosensitive layer and heated for at least one of the substrates during bonding is preferably carried out at a temperature of 70 ° C. to 130 DEG ° C., a pressure of about ^{0.1MPa~1.0MPa (1kgf / cm 2 ~10kgf /} cm 2 or so) It is preferable to pressure-bond with. These conditions are not particularly limited, and are appropriately selected as necessary. If the photosensitive layer is heated to 70 ° C. to 130 ° C., it is not necessary to pre-heat the substrate in advance. Adhesion and follow-up can be further improved by pre-heat treatment of the circuit forming substrate.

(Ii) Exposure step In the exposure step, at least a part of the photosensitive layer formed on the substrate as described above is irradiated with actinic rays, whereby the exposed portion irradiated with actinic rays is photocured. A latent image is formed. At this time, when the support existing on the photosensitive layer is transparent to the active light, the active light can be irradiated through the support. On the other hand, when the support is light-shielding against actinic rays, the photosensitive layer is irradiated with actinic rays after the support is removed.

    Examples of the exposure method include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork (mask exposure method). Alternatively, a method of irradiating actinic rays in an image form by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.

  The light source for actinic rays is not particularly limited, and a known light source can be used. For example, effective use of ultraviolet light, visible light, etc. such as carbon arc lamp, mercury vapor arc lamp, high pressure mercury lamp, xenon lamp, gas laser such as argon laser, solid state laser such as YAG laser, blue-violet laser such as semiconductor laser and gallium nitride What emits is used.

  The wavelength of the actinic ray (exposure wavelength) is preferably in the range of 340 nm to 430 nm, more preferably in the range of 350 nm to 420 nm, from the viewpoint of obtaining the effects of the present invention more reliably.

(Iii) Development Step In the development step, the uncured portion of the photosensitive layer is removed from the circuit forming substrate by development processing, whereby a resist pattern, which is a cured product obtained by photocuring the photosensitive layer, is formed on the substrate. . When the support is present on the photosensitive layer, the support is removed and then the unexposed portion is removed (development). Development processing includes wet development and dry development, and wet development is widely used.

  In the case of wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include a dipping method, a paddle method, a spray method, a method using brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of improving resolution, a high pressure spray method is preferable. You may develop by combining these 2 or more types of methods.

  A developing solution is suitably selected according to the structure of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution and an organic solvent developer.

  The alkaline aqueous solution is safe and stable when used as a developer, and has good operability. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate, and the like. Alkali metal phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, borax (sodium tetraborate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2 -Amino-2-hydroxymethyl-1,3-propanediol, 1,3-diamino-2-propanol, morpholine and the like are used.

  Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1% by mass to 5% by mass of potassium carbonate, and 0.1% by mass to 5% by mass of sodium hydroxide. A dilute solution of 0.1 mass% to 5 mass% of sodium tetraborate is preferred. The pH of the alkaline aqueous solution is preferably in the range of 9-11. The temperature is adjusted according to the alkali developability of the photosensitive layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.

  The alkaline aqueous solution may contain one or more organic solvents. Examples of the organic solvent to be used include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. . These are used alone or in combination of two or more. When the organic solvent is included, the content of the organic solvent is preferably 2% by mass to 90% by mass based on the alkaline aqueous solution. Moreover, the temperature can be adjusted according to alkali developability. A small amount of a surfactant, an antifoaming agent or the like may be mixed in the alkaline aqueous solution used for development.

  Examples of the organic solvent used in the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. It is preferable to add an organic solvent developer to these organic solvents in order to prevent ignition by adding water in the range of 1% by mass to 20% by mass.

The method for forming a resist pattern, by performing exposure after removing unexposed portions, energy heating or 0.2J ^/ cm ² ~10J ^/ cm 2 of 60 ° C. to 250 DEG ° C. If necessary, the resist A step of further curing the pattern may be further included.

[Method of manufacturing printed wiring board]
The method for producing a printed wiring board according to the present invention includes a resist pattern formed on a conductive layer of a substrate (circuit forming substrate) including an insulating layer and a conductive layer formed on the insulating layer by the above-described resist pattern forming method. A step of forming a conductor pattern by etching or plating the substrate on which is formed. The manufacturing method of a printed wiring board may include other processes, such as a resist removal process, as needed. Etching or plating of the substrate is performed on the conductor layer of the substrate using the formed resist pattern as a mask.

  In the etching process, using the resist pattern (cured resist) formed on the substrate as a mask, the conductor layer of the circuit forming substrate not covered with the cured resist is removed by etching to form a conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. Examples of the etching solution include a cupric chloride aqueous solution, a ferric chloride aqueous solution, an alkali etching solution, and a hydrogen peroxide etching solution. Among these, it is preferable to use a ferric chloride aqueous solution because it has a good etch factor.

  On the other hand, in the plating process, copper, solder, or the like is plated on the conductor layer of the circuit forming substrate that is not covered with the cured resist, using the resist pattern (cured resist) formed on the substrate as a mask. After the plating treatment, the hardened resist is removed, and the conductor layer covered with the hardened resist is etched to form a conductor pattern. The method of plating treatment may be electrolytic plating treatment or electroless plating treatment. The plating treatment includes copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, hard gold plating, and soft plating. Examples thereof include gold plating such as gold plating.

  After the etching process and the plating process, the resist pattern on the substrate is removed (peeled). The removal of the resist pattern can be performed, for example, using a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step. As this strongly alkaline aqueous solution, a 1% by mass to 10% by mass sodium hydroxide aqueous solution, a 1% by mass to 10% by mass potassium hydroxide aqueous solution and the like are used. Among these, it is preferable to use a 1% by mass to 10% by mass sodium hydroxide aqueous solution or a 1% by mass to 10% by mass potassium hydroxide aqueous solution, and a 1% by mass to 5% by mass sodium hydroxide aqueous solution or 1% by mass to 5% by mass water. It is more preferable to use an aqueous potassium oxide solution. Examples of the method of applying a strong alkaline aqueous solution to the resist pattern include an immersion method and a spray method. These may be used alone or in combination of two or more.

  When the resist pattern is removed after the plating process, a desired printed wiring board can be manufactured by further removing the conductor layer covered with the cured resist by the etching process and forming the conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. For example, the above-described etching solution can be applied.

  The printed wiring board manufacturing method of the present invention can be applied not only to a single-layer printed wiring board but also to a multilayer printed wiring board, and also to a printed wiring board having a small-diameter through hole. .

  The photosensitive resin composition of this embodiment can be used suitably for manufacture of a wiring board. That is, one of the preferred embodiments of the present invention includes ((A) a binder polymer having a structural unit derived from styrene, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D And a photosensitive resin composition containing a polyglycerin alkyl ester type surfactant, and application of the photosensitive resin composition containing the surfactant to the production of a printed wiring board.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

(Examples 1-4 and Comparative Examples 1-3)
[Synthesis of Binder Polymer (A-1)]
A solution obtained by mixing 160 g of methacrylic acid as a polymerizable monomer (monomer), 140 g of methyl methacrylate and 200 g of styrene (mass ratio 32/28/40) and 0.8 g of azobisisobutyronitrile. This was designated as “Solution a”.

  A solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 100 g of a mixed solution (mass ratio 3: 2) of 60 g of methyl cellosolve and 40 g of toluene was designated as “Solution b”.

  A flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube was charged with 400 g of a mixture of methyl cellosolve and toluene having a quantitative ratio of 6: 4, and nitrogen gas was blown into the flask. The mixture was heated with stirring, and the temperature was raised to 80 ° C.

  The solution a was added dropwise to the mixed solution in the flask over a period of 4 hours at a constant dropping rate, and then stirred at 80 ° C. for 2 hours. Next, the solution b was dropped into the solution in the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80 ° C. for 3 hours. Further, the solution in the flask was heated to 90 ° C. with stirring over 30 minutes, stirred at 90 ° C. for 2 hours, then cooled to room temperature to stop stirring, and the solution of the binder polymer (A-1) was removed. Obtained. Acetone was added to the binder polymer solution to prepare a nonvolatile component concentration (solid content concentration) of 50% by mass. In addition, the room temperature as used in the field of this invention means 25 degreeC.

  The weight average molecular weight of the binder polymer (A-1) was 45000, and the acid value was 208.7 mgKOH / g.

  The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.

GPC condition Pump: Hitachi L-6000 type (Hitachi, Ltd.)
Column: 3 in total, column specifications: 10.7 mmφ x 300 mm
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M (Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran Sample concentration: 120 mg of a resin solution having a NV (nonvolatile content concentration) of 50% by mass was sampled and dissolved in 5 mL of THF to prepare a sample.
Measurement temperature: 40 ° C
Injection volume: 200 μL
Pressure: 49Kgf / cm ² (4.8MPa)
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (Hitachi, Ltd.)

[Synthesis of Binder Polymers (A-2) and (A-3)]
As the polymerizable monomer (monomer), the binder polymer (A-2) was obtained in the same manner as in the case of obtaining a solution of the binder polymer (A-1) except that the materials shown in Table 1 were used in the mass ratio shown in the same table. ) And (A-3) were obtained.

  Table 1 shows the mass ratio (%), acid value, and weight average molecular weight of the polymerizable monomers (monomers) for the binder polymers (A-1) to (A-3). “-” Means not blended.

[Preparation of photosensitive resin composition]
In the binder polymer solution obtained above, in the blending amount (g) shown in Table 2 below, (B) component, (C) component, (D) component and additive, as well as 8 g acetone, 8 g toluene, and methanol. The photosensitive resin composition of Examples 1-4 and Comparative Examples 1-3 was prepared by mix | blending 8g, respectively. In addition, the compounding quantity of the binder polymer shown in Table 2 is the mass (nonvolatile content) of a non-volatile component. Details of each component shown in Table 2 are as follows. “-” Means not blended.

(B) Photopolymerizable compound FA-321M (manufactured by Hitachi Chemical Co., Ltd., product name): 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane FA-MECH (manufactured by Hitachi Chemical Co., Ltd., Product name): γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate 9G (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.): polyethylene glycol dimethacrylate

(C) Photopolymerization initiator 9-PA (manufactured by Nippon Steel Chemical Co., Ltd., product name): 9-phenylacridine

(D) Polyglycerin alkyl ester type surfactant G-1 (Unigri (registered trademark) GO-102R, manufactured by NOF Corporation): Polyglycerin fatty acid ester (in Table 2, “(D-1)” and displayed.)

Additives ・ LCV (Yamada Chemical Co., Ltd., product name): Leuco Crystal Violet ・ TPS (Sumitomo Seika Co., Ltd., product name): Tribromomethylphenylsulfone ・ MKG (Osaka Organic Chemical Co., Ltd., product name) ): Malachite Green

[Production of photosensitive element]
Next, the obtained photosensitive resin composition solution was uniformly applied onto a 16 μm thick polyethylene terephthalate film (product name “G2-16” manufactured by Teijin Limited), and a hot air convection dryer at 100 ° C. And dried with a protective film made of polyethylene (manufactured by Tamapoly Co., Ltd., product name “NF-13”) to obtain a photosensitive resin composition laminate (photosensitive element). The film thickness after drying of the photosensitive layer was 30 μm.

[Production of laminated substrate]
Subsequently, a 1.6 mm thick copper clad laminate (made by Hitachi Chemical Co., Ltd., trade name “MCL-E-67”) composed of a glass epoxy material and copper foil (thickness 35 μm) formed on both surfaces thereof. The copper surface was polished using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, washed with water, and then dried with an air stream. The copper-clad laminate (hereinafter referred to as “substrate”) is heated to 80 ° C., and the resulting photosensitive element is laminated (laminated) on the copper surfaces on both sides of the substrate for evaluation. Each laminated substrate was produced. Lamination was performed at a speed of 1.5 m / min so that the photosensitive layer of each photosensitive element was in close contact with each copper surface of the substrate while removing the protective layer using a heat roll at 110 ° C. Moreover, the heat roll pressure at the time of lamination was 0.4 Mpa.

The obtained laminated substrate was allowed to cool and when the temperature reached 23 ° C., on the polyethylene terephthalate film of the laminated substrate, a concentration region of 0.00 to 2.00, a concentration step of 0.05, a tablet size of 20 mm × 187 mm. A photo tool having a 41-step tablet having a size of 3 mm × 12 mm for each step was brought into close contact. Using a direct drawing exposure machine (Hitachi Via Mechanics Co., Ltd., “DE-1UH”) using a blue-violet laser diode having a wavelength of 405 nm as a light source, the photosensitive layer was exposed through a photo tool and a support.

[Evaluation of sensitivity]
After the exposure, the polyethylene terephthalate film was peeled from the laminated substrate, the photosensitive layer was exposed, and a 1% by mass aqueous sodium carbonate solution was sprayed at 30 ° C. for 60 seconds to remove unexposed portions. Thus, the resist pattern which consists of hardened | cured material of the photosensitive resin composition was formed on the copper surface of a board | substrate. The sensitivity of the photosensitive resin composition was evaluated by measuring the number of remaining steps (step number) of the step tablet obtained as a resist pattern (cured film). Sensitivity is indicated by an energy amount (unit: mJ / cm ² ) at which the number of step steps is 17, and the lower this value, the better the sensitivity. The results are shown in Table 3.

[Evaluation of resolution and adhesion]
The remaining 41-step tablet using a drawing pattern having a line width (L) / space width (S) (hereinafter referred to as “L / S”) of 3/3 to 30/30 (unit: μm) The photosensitive layer of the laminated substrate was exposed (drawn) with an energy amount of 17 steps. After the exposure, the same development processing as in the sensitivity evaluation was performed.

  After development, the space portion (unexposed portion) is removed without residue, and the line portion (exposed portion) is formed with the minimum value of the line width / space width values in the resist pattern formed without meandering and chipping. The resolution and adhesion were evaluated. A smaller value means better resolution and adhesion. The results are shown in Table 3.

[Evaluation of peelability]
Using a drawing pattern for forming a 45 mm × 65 mm rectangular cured film for peelability evaluation, exposure (drawing) is performed on the photosensitive layer of the laminated substrate with an energy amount that the remaining number of steps of the 41-step tablet is 17 steps. Went. After the exposure, the same development processing as in the sensitivity evaluation was performed.

  Then, 300 ml of 3.0 mass% NaOH aqueous solution (peeling liquid) was prepared at 50 ° C. in a beaker having a capacity of 400 ml. While the peeling solution was stirred at 200 rpm using a stirring bar having a length of 30 mm, the developed substrate was immersed in the peeling solution, and the time (unit: second) until the cured film was separated from the substrate was measured. In addition, it is evaluated that the longer the time until the cured film is separated from the substrate, the shorter the peeling time and the better the peelability. The results are shown in Table 3.

[Lamination evaluation]
Using an auto-cut laminator (Hitachi Chemical Electronics Co., Ltd., “HLM-A60”), the obtained photosensitive element was laminated (laminated) on the copper surfaces on both sides of the substrate. Lamination was performed at a speed of 1.5 m / min so that the photosensitive layer of each photosensitive element was in close contact with each copper surface of the substrate while removing the protective layer using a 120 ° C. heat roll. The heat roll pressure during lamination was 5 kgf / cm ² . Lamination of each photosensitive element was performed 200 times in succession, and the lamination was evaluated as good when it was possible to laminate without any problem, and the lamination was evaluated as laminating when there was a laminating defect due to wrinkles or a photosensitive element feeding error. The results are shown in Table 3.

As is apparent from Table 3, (A) a binder polymer having a structural unit derived from styrene, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a polyglycerin alkyl ester type. A resist pattern formed from a photosensitive resin composition containing a surfactant was excellent in sensitivity, resolution, adhesion, and peelability, and could be used without any problem with an auto-cut laminator. On the other hand, in Comparative Examples 1 to 3, it was difficult to achieve both resolution, adhesion, and laminating properties.

Claims (5)

  (A) a binder polymer having a structural unit derived from styrene, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a polyglycerin alkyl ester type surfactant. Photosensitive resin composition. The photosensitive resin composition of Claim 1 in which the said (B) photopolymerizable compound contains the compound represented by the following general formula (I).

[In Formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an ethyleneoxy group or a propyleneoxy group. _(XO) r _1, showing the _{(XO) r 2, (YO} ) s 1, and (YO) _{s 2,} respectively (poly) ethyleneoxy group or a (poly) propyleneoxy group. _{r 1,} r 2, _{s 1} and _{s 2} each independently represent 0-40. r ₁ , r ₂ , s ₁ and s ₂ represent the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. ]   A photosensitive element provided with a support body and the photosensitive layer formed from the photosensitive resin composition of Claim 1 or 2 provided on the said support body. A photosensitive layer forming step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to claim 1 or 2, or the photosensitive element according to claim 3,
An exposure step of irradiating at least a part of the photosensitive layer with actinic rays to cure the region;
A developing step of removing an unexposed portion other than the region of the photosensitive layer from the substrate;
A method for forming a resist pattern having   The manufacturing method of a printed wiring board including the process of etching or plating the board | substrate with which the resist pattern was formed by the method of Claim 4.